Process of and apparatus for making hydrogen.



A. MESSERSCHMITT. PROCESS OF AND APPARATUS FOR MAKING HYDROGEN.

APPLICATION FILED JUNE 12 I9I3.

PatentedAug. 31,1915.

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ANTON MESSERSGHMITT, OF STOLBERG, GERMANY.

rnocnss or arm arrnnn'rus FOR To all whom it may concern:

" Be it known that I, AN'roN Mnssnnsonmrm, a citizen of the German Empire, residing at Stolberg, in Rhineland, Germany, have 1nvented certain new and useful Improvements in Processes ofand Apparatus for Making Hydrogen, of which the following is a specification.

This invention relates tofprocess'es of and apparatus for making hydrogen; ,and it vcomprises a method of producing hydrogen by alternate reduction and steammg of-a ,f errugin'ous contact mass arranged as a col umn, or'as'successive layers, wherein such contact massis zonally reduced and heated,

- successivelayers or strata being succcessively reduced and the emerging reducing gases from each such layer or stratum bemg used to l impart combustion heat to the next succeed- 20 ing stratum priorto the. reductionof such next succeeding stratumand wherein zonal heating of successive layers is resorted to; and it further comprises a new organization ofelements comprisin a shaft or the like, a .column of pervious material therein, .means for, introducing steam at one end of said shaft, means for relength of said shaft; all as more fullyhere inafter set forth and as claimed.

' 'cip1e,'i's one which presents many difficultieson the large scale; these difliculties" being mainly those incident to heating. While the reducing and steaming or oxidation" reactions themselvesdo not absorb much heat, the alternate reduction and oxidation ofthe iron practically balancing thermally, yet, apart from radiation losses, the passage of; large volumes of gases and of steam through the apparatus carries away muchheat which must be replaced. And it is necessary to keep the reaction mass at a rather exact temperature. Overheating is apt to result in welding of the particles of spongy iron, with consequent diminution of porosity and active surface and, in the oxidizing pass, in

formation of slag by the oxid of iron 'un1t- ,ing with silica. and silicates, such as clay. I ,Underheating lessens production of hydro-1 lling of ferruginous Specification of-Iietters Patent. Patten-ted Aug", 311, 191115 Application filed June 12, 1913. Serial'No. 773,2(15.

gen and is also apt to cause a deposition of carbon in the reducing pass with possible a formation of iron carbids which will give evil-smellinghydrocarbons in the steaming stage. As capacity, or output, is dependent on the active surface exposed and on the quantity of gases and steam which can be contacted with suchsurface in a time unit, a

loose porous filling is necessary and this, porosity interferes materially with heating uniformly. Ordinarily, .the operation is conducted in a furnace-heated iron or steel;-

is the ratio. of heat "receiving surface to the active contents and the higher the tempera- 1r'etort,' usually] circular in crossrsection. 1 Necessarily, the larger is this retort, the less to the center of the reaction mass in a reasonable time. This is apt to result in overheating at the circumference of the reaction mass and also in a rapid deterioration ofthe retortIbythe oxidizing action o fthe furnace ases. 1 The re'torts for this reason are not of ong life; and particularly so since they fusing rapidlythrough even minute orifices. The same objection of the difficulty of comof a vertical column of such material with- 1 must be replacedas soon as any substantial I cracking orporosity appears, hydrogen difmovin hydrogen at the/other-endand a plurahty of means for introducing air: and. for introducing reducing gases located at a.-

.85 plurality of successive points along the out overheating the first layer where the draft current enters. The margin between -.the temperature which is'necessary for reaction and that which injures the materialis not great. I The effort is always to save timebyusing unduly heated draft currents. I y In the accompanyinginvention I have devised a method and means-forcarrying the necessary heat mto the mass without the ob-' jections obtainingboth to the use of an externally heated iron retort and of the usual 'type'of shaft furnace. In this invention I maintain a column of porous and channeled reaction material in-a suitable sha'ft or the like; this column and shaft being best vertically disposed; but in' lieu, of attempting to'heat allthe various successive layers se active reaction material.

through one layer by hot draft currents applied to the first layer in series, I heat these layers successively and methodically, heating'first the lowermost layer, then the next succeeding and so on until the various layers are at thedesired temperature. Reduction is performed in the same manner and by so doing I can secure a considerable economy, since I can use the reducing gas which. has passed through one layer and reduced the iron oxids therein but which is still freely combustible, for heating the next superimposed layer. For this purpose I cause such gas to burn in the pores, and

. as a matter of fact, inthe combustion there need be no excess of oxygen; there need be no such quantity of oxygen or air in excess as would injuriously afi'ect such contact mass. While gases burning with air in free space ordinarily require a considerable excess of air for rapid combustion, say, 10 to 20 per cent. over that theoretically necessary, this is not so with gas burning in direct contact with a catalytically acting material, as in the present instance where gas and air are burned together in the pores or channels of a contact mass. Sufficient combustion and development of heat may be attained even with a deficit of air; 11. e. where the emerging gases are. still combustible. In the present invention therefore I provide a shaft of some suitable refractory material. As no heating by conduction through its walls is to be performed, the shaft or chamber is advantageously made of masonry and has walls of refractory material of considerable thickness to reduce losses of heat by radiation. It may be advantageously heat-insulated. Within this chamber I place a column, or successive layers, of ferruginous reaction material in any desired manner which will afford free penetration of draft currents throughout the length of the column while at the same timeinsuring that such draft currents shall be in efiicient contact with the Advantageously, the shaft is lined .with iron to promote gas tightness. This iron liningwhile not indispoints I may channel or recess the wall of the chamber to form annular ducts or channels into which the connections for air and gas open. These connections are best so arranged as to discharge tangentially into these channels. If the contact materialis contained in the chamber 'as loose lumps, as it frequently is, by suitable arrangements the base ofeach sub-pile may extend into and on the base of this channel as an angle-0frepose pile, leaving the upper portion of the channel free and unobstructed for circumferential circulation of gas or air or of flame. Or the reaction mass may be contained in orificed steel or iron containers of suitable shape. With such a structure, presuming that a steaming and hydrogen producing stage is just ended and that the active surface of the contact mass is in the condition of oxrd, I may pass air and gas Into the lowermost annular channel in the series in such a way as to develop the necessary amount of heat in the proximate lateral 1 layer of contact mass. The products of combustion rise through the porous mass into the next succeeding upper layers and thence to a point of escape. This lowermost layer having received the desired number of heat units, the supply of air is cut off, while that of gas is continued. This gas now enters the hot contact mass and reduces it to metallic iron: This action being of the type of those known as mass actions, the reducing gas is not wholly oxidized in this reduction Rising into bustible, into the next succr eding upper layer where it is burned by air introduced at this point. This methodical operation is continued throughout the heightof the shaft.

In another method of operation, the lowermost layer may first be heated by circling flame, then the next and so on upward until all the material in the shaft is at the proper temperature. This being the case, gas is in troduced in the lowermost layer; then in the next layer and so on upward. In other words, heating and reductionare two separate operations.

In the accompanying illustration I have shown, more or less diagrammatically, an organization of apparatus elements within the present invention. In this showing Figure 1 is a central vertical section of one type of apparatus which may be used; and Fig. 2 is a fragmental horizontal section of the same '(along line a1--w of Fig. 1) at the point where pipes 16 and 20 enter.

In this showing, element 1 is a vertical shaft of masonry or the like. At various points along its height the inner, wall is channeled to afford annular recesses 2, 3,4 and 5. our of these recesses are shown, corresponding with :layers A, B, C and D of the reaction material. Doors 6, 7 8 and 9 communicate with these recesses. The inner wall may or may not be lined with iron or steel lining 10. This lining may be in one or several sections. Within this shaft is a column of reaction material which may be ganese also exercises a specific catalytic ac tion which isdesirable and further operates to prevent the deposition of carbon or' the formation of iron carbids should the reactionv mass temporarily run too cool. Artificial mixtures of manganese and iron. oxids may be used. In the arrangement of the column, the maintenance of the; porosity and perviousness of the column of material may be aided by the location at intervals of' iron or steel elements 11 across the column to box off the layers, each such box being provided with an internal filling of the same reaction mass and having a perforated top and bottom. As "shown, these boxes rest on ears or lugs entering the stated annular recesses. On each box is a pile of loose material which may enter the recess as an angleof-repose pile. Above the top of the uppermost pile may be sprung one or more perforated arches 12 of refractory brick to act as heat regenerators for a purpose later overheating. Asstated the porous material is not a very good conductor of heat. It is advantageous to construct the inner iron lining of the shaft, if used, with a vertical line of division. This enables disassemblage of the structure to an extent suflicient to take out the filling mass. For example, half the brick work in'the upper recesss may be taken out, the loose reaction mass having been first removed through door 6. The iron box may then be lifted out and replenished. On removing the loose pile of material below the top box, the next box may be lifted out in similar manner. To facilitate removal in this manner, it is better to make the boxes in downward succession of slightly decreasing width.

In the use of the described structure'presuming a steaming and hydrogen-producing stage just ended and replenishment of heat to be necessary, top cap 14. is removed. Air

and gas are introduced through 23 and 19. Ignition takes place with production of a circling heating flame sweeping around 5. The products of combustion pass inward and upward through the reaction mass, heating the layer D of material laterally next recess 5 and the material thereabove. As soon as-the layer D of material is heated suiliciently, introduction of air by 23 is stopped, the flow of gas through 19 being continued and introduction of air through 22' begun. The gas from 19 now reduces the reaction material of layer D and passes upwardly into layer-'C. where it is joined by the air from 22. The resultant combustion now heats layer 0. Introduction of gas at 19 and air at 22 now cease while gas is fed in at 18 and air is supplied at 21. Reduction of C and heating of B now take place. B is next reduced and A heated in a similar way. When A is hot introduction of air at 20 ceases and air is fed in at 30. The reducing gaspasses upward from A and is burnt in the diagrammatically shown checker I 12-by the air from 30. After the reduction.

of A, thehydrogen producing pass is begun.

Damper 14 is closed and steam from 15 allowed to flow downward through the column, displacing gases before it and forming hydrogen. The waste gases are vented at 26 and whensufliciently pure hydrogen appears, it is sent to a place ofuse through 28.

.At the end of the steaming stage, the described heating and reducing steps may be again performed. In another method of operating, combustion may be successively effected in channels 5, 4, 3 and 2, thereby heating the reaction mass uniformly from bottom to top; and then reduction effected by admitting reducing gas at 19 and allowing it to rise throu h the column, ultimately burning it by air 50m 30.

In an alternative method of operation, gas may be admitted at 19 with a modicum of air from 23. The amount of air may be from 10 to 20 per cent. of the volume of gas. Witha limited amount of the gas does not lose its power of reducing oxids of iron but under the catalytic effect of the reaction mass combustion to the extent permitted by the amount of air takes place in the reaction mass With concomitant development of heat in the place Where it is needed. The gas from D may be burnt in C as before and then gas With a limited amount of air admitted from 18 and 22; and so on up the column. Or after finishing the reduction of D, Without admitting air alone to C, a

current of gas from 18 With a modicum of air from 22 may be allowed to enter C; and

so on. Many other permutations and modifications are possible.

lVlll'lQ other gases, such as oil gas, natural gas, Mond gas, etc., may be used'in the heatmg and reduction stages, I find blue Water gas the most satisfactory.

The iron cross-elements 11 may be replaced by simple perforated cross plates or by bars, or may be omitted altogether. Their use is however advantageous.

What I claim is 1. In the manufacture'of hydrogen, the process Which comprises successively steaming, heating and reducing a pervious column of ferruginous reaction material, such heating being by application of combustion heat in a plurality of successive stages to a succession of layers of material along the length of such column.

2. In the manufacture of hydrogen, the process which comprises successively steaming, heating and reducing a pervious column of ferruginous reaction material, such heating being by application of combustion heat in a plurality of successive stages to a succession'of layers of material along the length of such column with development of combustion heat Within said material.

3. In the manufacture of hydrogen, the process which comprises successively steaming, heating'and reducing a pervious column of ferruginous reaction material, such heating being by applying a flame of gas and air circumferentially in contact -With a relatively short layer in such column.

4. In the manufacture of hydrogen by the alternate steaming and reduction of a pervious column of ferruginous reaction material, the process of reducing and heating such column which comprises producing an ignited flow of gas and air circumferential of a layer of the material in such column until such layer is heated to the desired degree, products of combustion being removed through such layer, and then cutting off the such column which comprises producing an ignited flow of gas and air circumferential of a layer of the material in such column until such layer is heated to the desired degree, products of combustion being removed through such layer, cutting off the flow of air While continuing the flow of gas until the heated layer is reduced and during such flow of gas into this layer admitting air to the next proximate layer to burn the efiluent gas from the layer undergoing reduction in said next proximate layer.

6. In the manufacture of hydrogen by the alternate steaming and reduction of a pervious column of ferruginous reaction material, the process of heating and reducing a column of such material which comprises passing currents of reducing gas successively into and through successive layers and burning the eiiiuent gas from each preceding layer by admission of air into the next succeeding layer, said operations being continued until the material of said column is heated and reduced from end to end.

7. In the manufacture of hydrogen by the alternate steaming and reduction of a pervious column of ferruginous material contained in a vertical shaft, the process of heating and reducing such column in a plurallty of stages which comprises heating an under layer, reducing the heated layer by introduction of reducing gas, burning the effluent gas from such layer in the next succeeding upper layer by introduction of air until heating thereof is eII'ected and then introducing gas into such next succeeding upper layer to reduce the same, this operation being repeated until all layers have been heated and reduced.

8. In the manufacture of hydrogen by the alternate steaming and reduction of a pervious column of ferruginous reaction material, the process of reducing and heating such column which comprises producing an ignited flow of gas With a httle air, the amount of such air being insuflicient for complete combustion, circumferential of a layer of the material in such column until such layer is heated to the desired degree, productsv of combustion being removed through such layer, and then cutting off the flow of air while continuing that of gas until the heated layer is reduced to' the desired degree.

9. In a hydrogen generating apparatus, a casing, a column of pervious ferruginous reaction material therein,-connections for introducing steam at one end, connections for removing hydrogen at the other, a plurality of means for introducing air at different points along said column and means for introducing reducing gas at each such point.

10. In a hydrogen generating apparatus, a Vertical shaft, a column of pervious ferruginous reaction material therein, connections for introducing steam at one end, connections for removing hydrogen at the other, a plurality of means for introducing air at different points along its height and means for introducing reducing gas at each such point.

11. In a hydrogen generating apparatus, a casing having a plurality of internal circumferential recesses in its wall, a column of pervious ferruginous reaction material arranged in the casing in such manner as to leave a free space therearound in each such recess, connections for introducing steam at one end, connections for removing hydrogen at the other, means for introducing air into each of said recesses and means for introducing reducing gas into each such recess.

12. In a hydrogen producing apparatus, a vertical shaft having a plurality of internal circumferential recesses at various points along its height, a pervious column of ferruginous material Within said shaft,

connections for introducing steam and for removing gases at its ends and means for introducing gas and for introducing air into each such recess.

13. In a hydrogen producing apparatus, a vertical shaft, a columnar filling of pervious ferruginous reaction material in said shaft, means for introducing steam at the top, means for removing Waste gases at the top, means for removing hydrogen at the base, a plurality of means for introducing reducing gas located at various points along its height and means for introducing air at each such point.

It. In a hydrogen producing apparatus, a vertical shaft, means for supporting a column of pervious ferruginous reaction material therein, a waste gas outlet near the top, a heat storing checker between said column and said outlet, means for passing steam through said checker, means for removing hydrogen near the base of the column, means for introducing reducing gas at a plurality of points along the height of said column and means for introducing air at such points.

15. In a hydrogen producing apparatus, a vertical shaft of refractory material having a plurality of circumferential recesses in its inner wall, means for supporting a column of pervious ferruginous reaction material in such shaft in such manner as to leave a clear circumferential space in each such recess, a waste gas outlet near the top, a heat storing checker between said column and said outlet, means for passing steam through said checker, means for removing hydrogen at the base of the column, means for introducing air into each such recess and means for introducing gas into each such recess.

In testimony whereof, I affix my signature in the presence of two subscribing Witnesses.

ANTON MESSERSCHMI'IT.

Witnesses MARTHA MESSERSCI-IMITT, CARL ANDREAS. 

